White-light promoted degradation of leucopterin and related pteridines dissolved in seawater, with evidence for involvement of complexation from major divalent cations of seawater

The photochemical instability of several related pteridines in seawater was investigated by aseptic incubation of solutions at 20–22°C under illumination from cool-white light of intensity 6 kerg cm⁻² sec⁻¹, and the chemical changes were spectrophotometrically monitored. All the pteridines showed markedly accelerated degradation from this illumination relative to their behaviour in total darkness.Pterin and lumazine were degraded very slowly with zero-order reaction kinetics, while the other pteridines photolysed rapidly (according to first-order kinetics) with decomposition rates increasing in the order dioxylumazine (2,4,6,7-tetrahydroxypteridine) < leucopterin < isoxanthopterin < xanthopterin < oxylumazine (2,4,6-trihydroxypteridine). Excepting leucopterin and dioxylumazine, the photolysis rates were attributable to the pH of seawater and not its salt content; this was also the case with oxylumazine which required the salt content of seawater for decomposition in darkness. Leucopterin and dioxylumazine (both 6,7-dihydroxylated pteridines) gave evidence of complexation with the major divalent cations (Ca²⁺, Mg²⁺) of seawater, by virtue of which their photolytic degradation rates were enhanced to magnitudes obtained in pH-10 buffer without seawater. It is proposed that such complexation produces structural forms of these pteridines analogous to their normal ionic forms at pH 10–12.The photolysis of the 6-hydroxylated pteridines (xanthopterin, oxylumazine) proceeded via intermediate formation of their corresponding 7-hydroxylated derivatives (leucopterin, dioxylumazine).     

Uptake and transformation of C-labelled tributyltin chloride by the dog-whelk, nucella lapillus: Importance of absorption from the diet

The importance of the diet as a source of tributyltin (TBT) in Nucella lapillus was studied using [¹⁴C]tributyltin chloride. In N. lapillus provided with prelabelled mussels, Mytilus edulis, in labelled water (mean 20·5 ng/litre TBT) the rate of accumulation of total ¹⁴C was 2–3 times that in unfed animals. Owing to its degradation in the tissues of both fed and unfed animals, concentrations of [¹⁴C]TBT tended to reach a plateau after only 28 days. However, total concentrations of ¹⁴C were still increasing after 49 days. Under experimental conditions (15°C, ample food, no disturbance) the diet accounted for about 50% of the body burden of TBT in N. lapillus after 49 days exposure: concentration factors (dry tissue/water) for [¹⁴C]TBT in both male and female N. lapillus were similar at about 60 000 in fed and 30 000 in unfed animals. It is concluded that the diet may contribute less than half of the body burden of TBT found in natural populations subjected to life-long exposure.     

The intertidal erosion rate of cohesive sediment: a case study from Long Island Sound

Over the past decades, many attempts have been made to generate useful bottom erosion models for the study of cohesive sediment movement. This study addresses some of the key questions involved in determining the functional relationship between erosion rate and bottom shear stress. Current, wave, and turbidity data were collected from a bottom mounted instrument array in a moderately energetic estuarine environment. The bottom shear stress was calculated from a wave–current interaction model. The erosion rate was derived from the observed sediment concentration using a vertical mixing model. Examination of the relationship between erosion rate and bottom stress showed that the erosion rate varied at intertidal frequency. When averaged over the tidal fluctuation, the erosion rate remained approximately constant at low stress, but increased sharply when the shear stress rose above a critical value. This suggests two-stage erosion. The bed has a layered structure, in which a thin layer of loose, high water content material overlies a more consolidated bed. The top layer of high water content material (fluff) was easily disturbed and re-suspended by tidal currents, but the consolidated bottom layer was eroded only under conditions of high shear stress.     

Trace metal-binding proteins in marine molluscs and crustaceans

Some marine invertebrates, such as the American oyster, Crassostrea virginica, the blue crab, callinectes sapidus and the American lobster, Homarusamericanus, concentrate trace metals in their tissues. The occurrence of metallothionein, a low molecular weight, sulfur-containing metal-binding protein, has been correlated with elevated levels of trace metals in these organisms. It is our hypothesis that, whilst metallothioneins are involved in the sequestration of elevated levels of trace metals, they primarily function in regulating normal metal metabolism. In this paper we describe recent field and laboratory experiments designed to examine how oysters, blue crabs and lobsters manage accumulated cadmium, copper and zinc. The possible rôles of metallothionein, as well as the tissue distribution of metals, are emphasized. Metallothioneins were found in all animals we examined; concentrations of metallothioneins and the the amount of bound trace metals are related to time of exposure. We have also demonstrated that the laboratory developed metallothionein models for blue crabs and lobsters may be useful in predicting the partitioning of trace metals in animals living in environments polluted with trace metals.     

Structural modeling and testing of a concrete canoe

A finite element model is set up and experimental tests are performed to help understand the behavior of a concrete canoe and subsequently optimize its design. First, the performance criteria that must be satisfied to participate at the annual ASCE/Master Builders competition are described. Then, the finite element model and the different loading cases that were studied are presented. Results from these loading cases are discussed and used to optimize the material properties as well as the thickness of the hull and the dimensions of the gunwale and reinforcing ribs. Static and dynamic experimental tests were also conducted to validate the results of the finite element analyses. The results indicate that the main stresses and strains are caused by the static load cases. The additional stresses caused during races are small.     

Paleomonsoon precipitation deduced from a sediment core from the equatorial Indian Ocean

Rapid shifts in past climate recorded in polar ice sheets have elicited various explanations relating to either thermohaline circulation changes by ice-rafting or natural greenhouse gas concentrations modulated by climatic conditions in the tropics. To compare the tropical paleoclimate record with the polar record, one must choose sediment cores from highly productive ocean regions. Necessarily, such regions reflect the wind records in the tropics, because high productivity is associated with upwelling driven by winds. Comparing tropical precipitation records with high-latitude records is, however, a more difficult task because sediments recording paleoprecipitation usually have low sedimentation rates, and offer coarser resolution relative to polar ice cores. Here, we present δ ¹⁸O data of three planktonic species of Foraminifera (a proxy for precipitation) from such a sediment core, spanning the past 35 ka for the equatorial Indian Ocean, which falls under the southwest monsoon (SWM) realm. Results show that minimum SWM precipitation occurred at the Last Glacial Maximum, with a subsequent increase at Termination IA. During the Holocene, SWM precipitation intensified uniformly up to the core top (∼2.2 ka b.p.), as revealed by generally decreasing δ ¹⁸O values. Variations in precipitation are consistent with climate changes recorded in polar ice sheets. Although the different resolutions of the two records preclude a rigorous comparison, abrupt cooling/warming events appear to be accompanied by sudden reduction/enhancement in (SWM) rainfall. Thus, mechanisms with time scales much shorter than a millennium, such as natural greenhouse warming (e.g., CH₄ concentration), controlled by emissions from the tropics, could have played a major role in high-latitude climate change.